O, o&#39;-dihydroxyazo dyestuffs and their metal complex compounds



United States Patent O 0,0'-DIHYDROXYAZO DYESTUFFSAND THEIR METAL COMPLEX COMPOUNDS Edgar Enders, Leverkusen-Bayerwerk, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany Application February 8, 1956v Serial No. 564,124

6 Claims. (Cl. 260-149) No Drawing,

0 X ll wherein X stands for a sulfamide or an alkyl sulfone radical, Y means hydrogen or a non-ionic substituent, and to the metal complex compounds, in particular the cobalt and chromium complexes of said azo dyestuffs.

It is an object of the present invention to provide new monoazo dyestuffs and their metal. complex compounds. It is a further object of; the. invention to provide new metal containing azodyestufls with good fastness properties.

The new metal-free azo dyestulfs may be obtained by coupling o-amino-hydroxy-benzenes which are substituted by a sulfamide oran alkyl sulfone group and which may bear further non-ionic substituents with indandione- (1,3) or with such derivatives thereof which form indandion-(1,3)- under the conditionsv of coupling e. g. indandione-(1,3)-2-carboxylic acid and its functional derivatives.

Suitable o-aminohydroxy-benzenes are e. g. l-amino- Z-hydroxy-benzene-S-sulfonamide, 1 -arnino 2 hydroxybenZene-S-sulfomethylamide, l-arnino 2 hydroxy-benzene-S-sulfo-ethylamide, l-amino-Z-hydroxy benzene-5- sulfo-butylamide, 1 amino-Z-hydroxy-benzene 5 sulfodimethylamide, l-amino-Z- hydroxy-benzene 5i sulf'odiethylamide, l-amino 2- hydroxy benzene 51- sulfo anilide, l-amino-Z-hydroxy benzene 4'-sulfo dimethylamide, l-amino-Z- hydroxy-benzene-S methylsulfone, 1- amino-Z-hydroxy-benzene-S-chloro-methylsulfone and 1- amino-2-hydroxy-benzene-S-ethylsulfone.

The metal-free azo dyestuffs dye wool by the afterchrome or meta-chrome process in brown shades of good wet-fastness properties and a good light fastness. They can be converted into their metal complex compounds, preferably into their cobalt and chromium complex compounds, alone or in mixture with other known metallizable azo dyestuffs. The metal containing dyestuffs dye wool, silk, polyamide fibres; and fibres of similar origin from neutral to weakly acid; baths in level red to brown shades of good fastness properties.

The following examples are given for the purpose of illustrating the invention, without, however, limiting it thereto; the parts being by weight if not otherwise stated. The parts by weight and the parts by volume stand in the ratio of grams to millilitres.

Example] 21.6 parts of 1-amino-2#hydroxy-benzene-S-sulfo-dimethylamide are dissolved in 250 parts by volume of water and 21 parts by-volume of concentrated hydrochloric acid and then diazotized at 0-5 C. with a solution of 7.5 parts of sodium nitrite in 20 parts by volume of water within one: hour. After the addition of a little amidosulfonic acid, the; diazo salt solution is combined with a suspension of 14 parts of indandione-(1,3). in 100 parts by volume of water; Concentrated ammonia is then added dropwise at. 5-10" C. until the reaction proceeds permanently alkaline. When coupling has finished, the mixture is heated: to 6070 C. and the dyestufi is precipitated by addition of acid and then filtered. It corresponds to the following formula:

The filter cake thus obtained is dissolved in 800 parts by volume of water with the addition of sodium hydroxide and then mixed while stirring with an ammoniacal solution of 13 partsof crystalline cobalt chloride at -95 C. When metallization is complete, the metal containing dyestufi is precipitated by addition of common salt, separated by. pressing and dried. It represents a brown powder whichdyes wool from neutral bath in. levelv red-brown. shades with good, fastness properties The corresponding chromium complex which can be obtained by known methods dyes wool from neutral bath reddish dark brown shadesthe fastness to light of which is slightly lower than of the dyeings obtained with the cobalt complex.

Dyestuifs with similar" properties are obtained if 1- amio-2-hydroxy-benzene-5' sulfo-diethylamide or l-am- ,ino-2=hydroxy-benzene-5-sulfo-methyl oxethylamide are used as diazo'compound's.

Example 2 20 parts of phthalyl acetic acid are introduced into a solution of 7' parts ofsodium in 200 parts by volume of absolute alcohol; dissolution. occurs with spontaneous heating. Thesodium salt of indandione-(l,3)-2-carboxylic acid thus obtained precipitates after a short time. 200-parts byvolume of water and subsequently at 05 C; a diazosa-lt solution obtained in customary manner from 202 parts of 1-amino-2-hydroxy-benzene- S-sulfo-methylamide are added. Then concentrated ammonia is added dropwise until the reaction proceeds permanently alkaline. When coupling is complete, the mixture is heated to 60-70.? C. and the dyestuff precipitated by addition of acid and filtered. It corresponds to the following formula:

The dyestuif is converted into its cobalt complex compound in the samemanner: as described in Example 1.

The cobalt containing dyestuif. represents a brown powder which dissolves in water with red-brown coloration and dyes woolfrom neutral bath in level red-brown shades with good fastness properties.

The corresponding chromium complex dyes wool'from neutral bath in levelreddish darkbrown shades.

3 Dyeings of similar properties are obtained if l-amino- 2 hydroxy-benzene-S-sulfo-ethylamide, 1 amino 2-hydroxy-benzene-5-sulfo N butylamide, 1 amino-Z-hydroxy-benzene-S-sulfoanilide or 1-amino-2 hydroxybenzene-S-sulfonamide are used as diazo compounds.

Example 3 18.7 parts of. 1-amino-2-hydroxy-benzene-5-methylsulfone are diazotized in usual manner and combined with a suspension of 14 parts of indandione-(l,3) in 100 parts by volume of water. Concentrated ammonia is dropped into the mixture at -5 C. until the reaction proceeds permanently alkaline. When coupling has finished, the mixture is heated to 60-70 C., the dyestufi' is separated by addition of acid and filtered. It corresponds to the formula:

The dyestuff is converted into its cobalt complex in the manner described in Example 1.

The cobalt containing azo dyestuff represents a brown powder which dissolves in water with red-brown coloration and dyes wool from neutral bath in level red-brown shades with good fastness properties.

If l-amino-Z-hydroxy-benzene S-chloro-methylsulfone or 1-amino2-hydroxy-benzene-S-ethyl-sulfone are used as diazo compounds, dyestuffs of similar properties are obtained.

Example 4 9.5 parts of 1-amino-2-hydroxy-benzene-4-sulfo-dimethylamide are dissolved in 3.1 parts of sodium nitrite and 5 parts by volume of 40% sodium hydroxide in 50 parts by volume of water. This solution is added to parts by volume of concentrated hydrochloric acid and 80 parts by volume of ice water at 0-5 C. The formed diazo compound partly precipitates in yellow crystalline form. When diazotization is complete, the mixture is combined with a suspension of 6.5 parts of indandione-( 1,3) in 200 parts by volume of ice water. Concentrated ammonia is dropped into the mixture until the reaction proceeds permanently alkaline. pling has finished, the mixture is heated to 60-70" C.,

When couthe dyestufi is precipitated byaddition of common salt,

isolated by pressing and dried. It corresponds to the which dyes wool from neutral bath in level bluish red shades with good fastness to wet processing and light. The corresponding chromium complex dyes wool in reddish brown shades with good fastness properties.

Dyestuffs of similar properties are obtained when using the following diazo compounds and coupling them with indandione-( 1,3

diazo compounds azo compounds metal shades on (5) l-amino-2-hydroxy-5-chloroindandione-(1,3) Cr violet benzene-4-sulfonamide. brown. (6) 1-amino-2-hydroxy-5-chlorodo Co red-brown.

benzene-4-sulfonarnide. (7) 1 amino 2 hydroxy 5 Go Do.

gethylbenzene 4 sulfonam- 1 e. (8) l amino 2 hydroxy -ben do 00 Do. zene 5 sulfo o methoxyanilide. (9) 1 amino 2 hydroxy -ben do C0 D0.

zone 5 sulfo 0 chloroanl llde. (10) 1 amino 2 hydroxy do Go Do.

benzene 5 sulfo o methylanilide. (11) 1 amino 2 hydtoxy do Go Do.

benzene 5 sult'o 1 methoxy-propylamide. (12) 1 amino 2 hydroxy do C0 D0.

5 sulfo (3' methane sulfonylaminoyanillde- I (13) 1 amino 2 hydroxy do Go Do.

benzene--sulfo-anilide. v (14) 1 amino 2 hydroxy -.do C0 D0.

benzene 5 sulfo 'y hydroxy-propylamld.

I claim:

1. A dyestufi selected from the group consisting of monoazo dyestuffs corresponding to the following formula wherein X is a member selected from the group consisting of a sulfonamide, methylsulfone and ethylsulfone radicals, and Y is a member selected from the group consisting of hydrogen, chlorine, and methyl; the chromium complex thereof and the cobalt complex thereof.

2. The cobalt complex of the dyestufi corresponding to the following formula:

3. The cobalt complex of the dyestuff corresponding to the following formula:

. 5 v I l 4. The chromium complex of the dyestufi correspond- 6. The cobalt complex of the dyestufi corresponding ing to the following formula: to the following formula:

HO HO OH 5 OH N=N--C\ N=NC\ SO:N.CH; c r SOgNHCHzCHCHaOH Hr-CHz-OH g 10 5. The cobalt complex of the dyestufl corresponding to References Cited in the file of this Patent the following formula:

no UNITED STATES PATENTS OH 1 1,233,433' Wuth et a1. July 17, 1917 15 2,673,199 Widmer et a1 Mar. 23, 1954 -N=N-C OaNHCHzOHsCIhO CH: C 

1. A DYESTUFF SELECTED FROM THE GROUP CONSISTING OF MONOAZO DYESTUFFS CORRESPONDING TO THE FOLLOWING FORMULA 